WO2001014307A1 - Cristaux colonnaires d'acide 6-hydroxy-2-naphtoique, et procede de production associe - Google Patents

Cristaux colonnaires d'acide 6-hydroxy-2-naphtoique, et procede de production associe Download PDF

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Publication number
WO2001014307A1
WO2001014307A1 PCT/JP2000/005535 JP0005535W WO0114307A1 WO 2001014307 A1 WO2001014307 A1 WO 2001014307A1 JP 0005535 W JP0005535 W JP 0005535W WO 0114307 A1 WO0114307 A1 WO 0114307A1
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WO
WIPO (PCT)
Prior art keywords
hydroxy
naphthoic acid
crystals
columnar crystals
aqueous medium
Prior art date
Application number
PCT/JP2000/005535
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English (en)
Japanese (ja)
Inventor
Ryuzo Ueno
Masaya Kitayama
Hiroyuki Kato
Ryoichi Otsuka
Original Assignee
Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo filed Critical Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo
Priority to EP00953491A priority Critical patent/EP1123914B1/fr
Priority to US09/830,119 priority patent/US6451109B1/en
Priority to CA002348401A priority patent/CA2348401A1/fr
Priority to JP2001518400A priority patent/JP3533386B2/ja
Priority to DE60034020T priority patent/DE60034020T2/de
Publication of WO2001014307A1 publication Critical patent/WO2001014307A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions

Definitions

  • the present invention relates to columnar crystals of 6-hydroxy-2-naphthoic acid and a method for producing the same.
  • 6-Hydroxy-2-naphthoic acid is used as a raw material for various industrial materials, especially dyes, pigments and resins.
  • This compound is usually obtained by recrystallizing the compound obtained by the Kolbe-Schmidt reaction with water or a water / alcohol solvent.
  • the crystals obtained in this way are thin scales, have a small apparent specific gravity, a large angle of repose, and low fluidity. Therefore, there was a problem that the handling properties of the product, especially the transportability, the filling property, and the storage property were poor.
  • the present invention provides a method for obtaining 6_hydroxy-2-naphthoic acid having a high apparent specific gravity and excellent fluidity. According to the present invention, the handling property of the product, which has been a problem in the past, especially the transportability, the filling property, and the storage property are improved.
  • crude 6-hydroxy-12-naphthoic acid is dissolved in an aqueous medium, 3-hydroxy-1,2-naphthoic acid crystals are added as seed crystals, and the crystals are precipitated by cooling.
  • a process for preparing columnar crystals of 6-hydroxy-2-naphthoic acid comprising the steps of:
  • the present invention provides a method for dissolving crude 6-hydroxy-2-naphthoic acid in an aqueous medium, adding columnar crystals of 6-hydroxy-2-naphthoic acid as seed crystals, and cooling to precipitate crystals.
  • a process for preparing columnar crystals of 6-hydroxy-2-naphthoic acid comprising the steps of:
  • the present invention relates to a columnar crystal of 6-hydroxy-12-naphthoic acid having an X-ray diffraction peak 2 ° in the range of 16.8 to 17.8 and Z or 21.3 to 22.3. I will provide a.
  • FIG. 1 is a chart showing the results of X-ray measurement of purified 6-hydroxy-2-naphthoic acid of Example 1.
  • FIG. 2 is a chart showing an X-ray measurement result of purified 6-hydroxy-2-naphthoic acid of Example 2.
  • FIG. 3 is a chart showing the X-ray measurement results of the purified 6-hydroxy-2-naphthoic acid of Comparative Example 1.
  • FIG. 4 is a chart showing an X-ray measurement result of the purified 6-hydroxy-2-naphthoic acid of Example 3.
  • FIG. 5 is a chart showing X-ray measurement results of purified 6-hydroxy-2-naphthoic acid of Comparative Example 2.
  • FIG. 6 is a chart showing the results of X-ray measurement of the purified 6-hydroxy-2-naphthoic acid of Example 4.
  • FIG. 5 is a chart showing the results of X-ray measurement of purified 6-hydroxy-2-naphthoic acid of Comparative Example 3.
  • FIG. 8 is a chart showing the X-ray measurement results of the purified 6-hydroxy-2-naphthoic acid of Comparative Example 4.
  • FIG. 9 is a chart showing the results of X-ray measurement of purified 6-hydroxy-12-naphthoic acid of Example 5.
  • the columnar crystals of 6-hydroxy-2-naphthoic acid of the present invention can be prepared by recrystallizing crude 6-hydroxy-2-naphthoic acid produced by a general method such as the Kolbeschmidt method.
  • Used crude 6 arsenide Dorokishi 2 Nafute acid typically includes a 6-hydrate port carboxymethyl one 2- Nafute acid 8 0 wt 0/0 above, 3-hydroxy-one 2, 7 _ naphthoquinone Tesan, 2-hydroxy-1 one Naphthoic acid, unreacted] 3 Contains naphthol as impurities.
  • this 6-hydroxy-12-naphthoic acid for dyes and pigments, it is preferable to purify it to a purity of 98% by weight or more.
  • an aqueous medium is used to recrystallize the crude 6-hydroxy-2-naphthoic acid.
  • the aqueous medium is not particularly limited, but may be water or water-soluble.
  • Organic solvents may be used alone or in combination.
  • the water-soluble organic solvent include, for example, a mixed solvent of lower alcohols such as methanol, ethanol, and isopropanol, and an alkaline aqueous medium, for example, an aqueous hydration solution.
  • a mixed solvent of water and a lower alcohol particularly methanol
  • the mixing ratio of water and alcohol is not particularly limited, but a mixture of alcohol in an amount of 5 to 300 parts by weight, more preferably 20 to 15 parts by weight, per 100 parts by weight of water. Solvents are preferably used.
  • an alkaline aqueous medium for example, an aqueous solution of potassium hydroxide is used, it is appropriate to use 0.01 to 0.2 N, more preferably 0.01 to 0.05 N.
  • the aqueous medium may contain both an alkaline substance and a lower alcohol.
  • the aqueous medium may further contain dioxane / tetrahydrofuran or the like.
  • crude 6-hydroxy-2-naphthoic acid is introduced into an aqueous medium and heated to an appropriate temperature to completely dissolve 6-hydroxy-2-naphthoic acid.
  • the aqueous medium is preferably used in an amount of 1 to 20 parts by weight, particularly 3 to 10 parts by weight, based on 1 part by weight of the crude 6-hydroxy-2-naphthoic acid.
  • the heating temperature may be a temperature at which 6-hydroxy-12-naphthoic acid is completely dissolved, and may be appropriately selected depending on the aqueous medium used. Those skilled in the art can easily make such a selection.
  • the aqueous medium is a mixed solvent of water and alcohol, the heating temperature is appropriately selected within the range of 50 to 180 ° C. depending on the type and proportion of the solvent.
  • pressure may be applied when heating the aqueous medium, and the pressurizing condition varies depending on the type and ratio of the aqueous medium to be used.
  • the pressure is preferably set to 0.2 to 1.0 OMPa (gauge pressure). Is good.
  • a seed crystal is added to dissolved 6-hydroxy-12-naphthoic acid and recrystallized. If 3-hydroxy-1,2,7-naphthoic acid particles are used as seed crystals, columnar crystals of 6-hydroxy-2-naphthoic acid can be obtained.
  • the shape of the 3-hydroxy-2,7-naphthoic acid seed crystal is not particularly limited.
  • seed The size of the crystals is preferably 1 mm or less, preferably 0.2 mm or less, particularly preferably 0.05 mm or less in terms of spherical particle diameter.
  • columnar crystals of 6-hydroxy-12-naphthoic acid may be used as seed crystals.
  • the columnar crystals of 6-hydroxy-12-naphthoic acid used as seed crystals may be prepared by the method of the present invention.
  • the size of the columnar crystal of 6-hydroxy-1-naphthoic acid is 1 mm or less, preferably 0.2 mm or less, particularly preferably 0.05 mm or less in terms of spherical particle diameter. It is good to add.
  • columnar crystals of 6-hydroxy-12-naphthoic acid are particularly preferably used as seed crystals.
  • the amount of seed crystal added should be 6—hydroxy 2 to be purified.
  • the 6-hydroxy-2-naphthoic acid solution is preferably adjusted to a temperature around the saturation temperature of the solution, particularly within 3 ° C of the soil at the saturation temperature.
  • the solution is cooled slowly with gentle stirring.
  • the solution cooled to the predetermined temperature is aged while stirring or stopping the stirring while maintaining the temperature.
  • the aging temperature is not particularly limited, but it is convenient to set arbitrarily within the range of 20 to 100 ° C. according to the temperature of the subsequent filtration and separation step.
  • the aging time may be arbitrarily set depending on the state of crystal precipitation, but is generally 5 to 180 minutes.
  • the precipitated crystals are washed, filtered and dried by a conventional method. Specifically, for example, the obtained crystals are washed with water, and those obtained by centrifugal filtration using a filter cloth are dried by hot air drying.
  • the second embodiment of the present invention using the obtained columnar crystals as seed crystals may be repeated until the required purity is obtained.
  • 6-Hydroxy-1-naphthoic acid generally obtained is a thin flaky crystal
  • 6-hydroxy-2-naphthoic acid obtained by the method of the present invention is a columnar crystal and has the following properties.
  • Crystal appearance columnar crystal Representative value of X-ray diffraction peak 2 ⁇ : 16.8 to: 17.8 and / or 21.3 to 22.3
  • Decay angle 25 to 35 degrees (conventional scale: about 32 to 45 degrees)
  • Spatula angle average 30 to 55 degrees (conventional scale: about 60 to 75 degrees)
  • Fluidity index 50 to 65 (conventional scale: about 25 to 35)
  • the values in parentheses are the values of scaly crystals obtained by a conventional method. Since the X-ray diffraction values are significantly different from the scales obtained by the conventional method, it is clear that the crystal structure is essentially different from the conventional one.
  • the apparent specific gravity is high, the storage and transport volume can be reduced accordingly, and the flowability increases, so that the bridge clogging in the hopper and the adhesion trouble of the transport pipe are reduced. , Conveying on a conveyor becomes easy. Therefore, the filling operation becomes easier.
  • a 1-liter autoclave was charged with 90 g of 6-hydroxy-12-naphthoic acid and 450 g of water, and the temperature was raised to 150 ° C (gauge pressure 0.42 MPa). —Hydroxy-1-naphthoic acid solution was obtained.
  • 2.7 g of 3-hydroxy 2,71-naphthoic acid manufactured by Ueno Pharmaceutical Co., Ltd.
  • a particle size of about 30 m produced by the Kolbe-Schmidt method was added as a seed crystal, and 0.5 ° C was added.
  • the mixture was cooled to 80 ° C at a rate of / min, and aged at that temperature for 30 minutes for crystallization.
  • X-ray measurement was performed under the following conditions.
  • Measuring device RI NT- 1500 (manufactured by Rigaku Corporation)
  • UV wavelength 229 nm
  • Example 2 The crude 6-hydroxy-12-naphthoic acid was purified in the same manner as in Example 2 except that no seed crystal was used, to obtain 90 g of flaky crystals.
  • Figure 3 shows the X-ray diffraction measurement results of the obtained scaly crystals, Table 1 shows the typical X-ray diffraction angles of 20, Table 2 shows the composition, and Table 3 shows the particle size distribution. Table 3 shows the raw values of various products.
  • 100 g of scaly crystals were obtained in the same manner as in Example 2 except that 100 g of the scaly crystals obtained in Comparative Example 1 was used as a starting material, and the scaly crystals obtained in Comparative Example 1 were used as seed crystals.
  • the X-ray diffraction measurement results of the obtained scaly crystals are shown in Fig. 5, the typical X-ray diffraction angle 2 ⁇ is shown in Table 1, the composition is shown in Table 2, the particle size distribution is shown in Table 3, and various physical property values are shown in Table 4. Show.
  • a 1 liter capacity kolben was charged with 100 g of the scaly crystals of 6-hydroxy-l-naphthoic acid obtained in Comparative Example 1, 100 g of water, and 32 g of methanol, and 7 g of methanol. The temperature was raised to 5 ° C to obtain a 6-hydroxy-12-naphthoic acid solution. To this solution, 1 g of columnar crystals of 6-hydroxy-2-naphthoic acid having a particle diameter of about 100 ⁇ m prepared in Example 1 was added as seed crystals, and the solution was added at a rate of 0.5 ° CZ for 25 ° C. The mixture was cooled to C, and aged at that temperature for 30 minutes for crystallization.
  • Fig. 6 shows the results of X-ray diffraction measurement of the obtained columnar crystals
  • Table 1 shows typical X-ray diffraction angles of 2 ⁇
  • Table 2 shows Ito-Katari
  • Table 3 shows the particle size distribution
  • Table 3 shows various physical property values. See Figure 4.
  • scaly crystals 90 g were obtained in the same manner as in Example 4, except that the seed crystals were the scaly crystals obtained in Comparative Example 1.
  • Fig. 7 shows the X-ray diffraction measurement results of the obtained scaly crystals
  • Table 1 shows the typical X-ray diffraction angles of 2 ⁇
  • Table 2 shows the composition
  • Table 3 shows the particle size distribution
  • Table 4 shows the various physical properties. Show.
  • Table 5 shows the composition of the obtained columnar crystals and a typical X-ray diffraction angle of 2 °
  • Table 6 shows the particle size distribution
  • Table 8 shows various physical property values.
  • Example 6 Except that no seed crystal was used, the crude 6-hydroxy-2-naphthoic acid was purified in the same manner as in Example 6 to obtain flake crystals.
  • Table 5 shows the composition and representative X-ray diffraction angle of 2 mm of the obtained squamous crystal, Table 6 shows the particle size distribution, and Table 8 shows various physical property values.
  • Example 7 The columnar crystals obtained in Example 6 were sieved to obtain 12 g of a particle size-adjusted product having a particle size distribution shown in Table 7. The physical properties of the particle-size-adjusted product were measured in the same manner as in Example 6. Table 8 shows the results.
  • Measuring device Powder tester PT-N type (manufactured by Hosokawa Micron)
  • the liquidity index is a numerical evaluation of liquidity. Larger values indicate higher liquidity.
  • columnar crystals of 6-hydroxy-2-naphthoic acid which are used as raw materials for various industrial raw materials, in particular, dyes, pigments, resins and the like, are obtained.
  • the columnar crystals of 6-hydroxy-2-naphthoic acid according to the present invention have a high apparent specific gravity and excellent fluidity, so that the handling properties of the products, which have been a problem in the past, especially the transportability, the filling property, and the storage property, are improved. It is improved.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production de cristaux colonnaires d'acide 6-hydroxy-2-naphtoïque, consistant à dissoudre de l'acide 6-hydroxy-2-naphtoïque brut dans un milieu aqueux, à ajouter à la solution des germes cristallins d'acide 3-hydroxy-2,7-naphtoïque ou des germes cristallins colonnaires à la solution, et à refroidir le mélange obtenu pour réaliser une cristallisation. L'invention concerne également des cristaux colonnaires d'acide 6-hydroxy-2-naphtoïque produits conformément audit procédé, lesquels cristaux présentent, en diffraction aux rayons X, un pic 2υ compris entre 16,8 et 17,8 et/ou entre 21,3 et 22,3, et ont une gravité spécifique apparente élevée et une excellente fluidité.
PCT/JP2000/005535 1999-08-24 2000-08-18 Cristaux colonnaires d'acide 6-hydroxy-2-naphtoique, et procede de production associe WO2001014307A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP00953491A EP1123914B1 (fr) 1999-08-24 2000-08-18 Cristaux colonnaires d'acide 6-hydroxy-2-naphtoique, et procede de production associe
US09/830,119 US6451109B1 (en) 1999-08-24 2000-08-18 Columnar crystals of 6-hydroxy-2-naphthoic acid and process for manufacturing the same
CA002348401A CA2348401A1 (fr) 1999-08-24 2000-08-18 Cristaux colonnaires d'acide 6-hydroxy-2-naphtoique, et procede de production associe
JP2001518400A JP3533386B2 (ja) 1999-08-24 2000-08-18 ６−ヒドロキシ−２−ナフトエ酸柱状晶およびその製法
DE60034020T DE60034020T2 (de) 1999-08-24 2000-08-18 Säulenförmige Kristalle von 6-Hydroxy-2-naphthylsäure und ein Verfahren zu ihrer Herstellung

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11/236951 1999-08-24
JP23695199 1999-08-24

Publications (1)

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WO2001014307A1 true WO2001014307A1 (fr) 2001-03-01

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PCT/JP2000/005535 WO2001014307A1 (fr) 1999-08-24 2000-08-18 Cristaux colonnaires d'acide 6-hydroxy-2-naphtoique, et procede de production associe

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US (1) US6451109B1 (fr)
EP (1) EP1123914B1 (fr)
JP (1) JP3533386B2 (fr)
KR (1) KR100707752B1 (fr)
CN (1) CN100519502C (fr)
AT (1) ATE357426T1 (fr)
CA (1) CA2348401A1 (fr)
DE (1) DE60034020T2 (fr)
TW (1) TW527451B (fr)
WO (1) WO2001014307A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002322109A (ja) * 2001-04-20 2002-11-08 Ueno Seiyaku Oyo Kenkyusho:Kk ナフトール誘導体の造粒物およびその製法
WO2011115136A1 (fr) * 2010-03-16 2011-09-22 三菱化学株式会社 Procédé pour la production d'acide succinique

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1449821B1 (fr) * 2001-11-30 2012-05-09 Nippon Shokubai Co., Ltd. Acide mandelique optiquement actif et son derive, et procede de cristallisation correspondant
CN102173988B (zh) * 2011-03-25 2013-05-01 衢州英特高分子材料有限公司 一种6-羟基-2-萘甲酸的纯化方法
CN103360242A (zh) * 2012-04-09 2013-10-23 盐城拜克化学工业有限公司 一种6-羟基-2-萘甲酸的制备方法
CN102659576A (zh) * 2012-05-02 2012-09-12 苏州思睿屹新材料股份有限公司 2-羟基-6-萘甲酸的精制方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4057576A (en) * 1974-06-04 1977-11-08 Hoechst Aktiengesellschaft Process for isolating 2-hydroxynaphthalene carboxylic acids from reaction mixtures of the alkali metal salts of 2-hydroxynaphthalene with carbon dioxide
EP0325925A1 (fr) * 1988-01-15 1989-08-02 Hoechst Aktiengesellschaft Procédé pour l'épuration de l'acide naphtalène-2-hydroxy-6-carboxylique

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10120624A (ja) * 1996-10-18 1998-05-12 Sugai Kagaku Kogyo Kk ２−ヒドロキシナフタレン−６−カルボン酸の精製方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4057576A (en) * 1974-06-04 1977-11-08 Hoechst Aktiengesellschaft Process for isolating 2-hydroxynaphthalene carboxylic acids from reaction mixtures of the alkali metal salts of 2-hydroxynaphthalene with carbon dioxide
EP0325925A1 (fr) * 1988-01-15 1989-08-02 Hoechst Aktiengesellschaft Procédé pour l'épuration de l'acide naphtalène-2-hydroxy-6-carboxylique

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002322109A (ja) * 2001-04-20 2002-11-08 Ueno Seiyaku Oyo Kenkyusho:Kk ナフトール誘導体の造粒物およびその製法
WO2011115136A1 (fr) * 2010-03-16 2011-09-22 三菱化学株式会社 Procédé pour la production d'acide succinique
JPWO2011115136A1 (ja) * 2010-03-16 2013-06-27 三菱化学株式会社 コハク酸の製造方法
US9035095B2 (en) 2010-03-16 2015-05-19 Mitsubishi Chemical Corporation Processes for producing succinic acid

Also Published As

Publication number Publication date
EP1123914B1 (fr) 2007-03-21
CA2348401A1 (fr) 2001-03-01
TW527451B (en) 2003-04-11
JP3533386B2 (ja) 2004-05-31
DE60034020T2 (de) 2007-12-13
EP1123914A1 (fr) 2001-08-16
EP1123914A4 (fr) 2005-06-08
CN1335832A (zh) 2002-02-13
DE60034020D1 (de) 2007-05-03
KR20010080213A (ko) 2001-08-22
US6451109B1 (en) 2002-09-17
CN100519502C (zh) 2009-07-29
ATE357426T1 (de) 2007-04-15
KR100707752B1 (ko) 2007-04-17

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